Black‐Swan‐Ereignisse in der organischen Synthese

Nugent, William A.

doi:10.1002/ange.201202348

Cited by 10 publications

(3 citation statements)

References 160 publications

(109 reference statements)

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“…The air-and water-stability of gold catalysts, coupled with their ability to promote complex transformations under mild conditions has attracted considerable interest from the academic community. [1] Despite the rapid pace of recent developments, the majority of gold-catalyzed processes rely on a select few reaction manifolds: 1) Lewis acid catalysis, 2) p-activation, and 3) the generation of carbenoid intermediates (Scheme 1 A). [2] While these modes of reactivity have yielded important catalytic methodologies of broad scope and synthetic utility, [3] they are typified by catalytic cycles wherein gold maintains a +1 oxidation state, in stark contrast to the 2electron redox cycles characteristic of late transition metal catalysis.…”

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confidence: 99%

Gold‐Catalyzed Allylation of Aryl Boronic Acids: Accessing Cross‐Coupling Reactivity with Gold

2014

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A sp3 – sp2 C-C cross-coupling reaction catalyzed by gold in the absence of a sacrificial oxidant is described. Vital to the success of this method is the implementation of a bimetallic catalyst bearing a bis(phosphino)amine ligand. A mechanistic hypothesis is presented, and observable transmetallation, C-Br oxidative addition, and C-C reductive elimination in a model gold complex are shown. We expect that this method will serve as a platform for the development of novel transformations involving redox-active gold catalysts.

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confidence: 99%

Gold‐Catalyzed Allylation of Aryl Boronic Acids: Accessing Cross‐Coupling Reactivity with Gold

2014

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“…The air‐ and water‐stability of gold catalysts, coupled with their ability to promote complex transformations under mild conditions has attracted considerable interest from the academic community 1. Despite the rapid pace of recent developments, the majority of gold‐catalyzed processes rely on a select few reaction manifolds: 1) Lewis acid catalysis, 2) π‐activation, and 3) the generation of carbenoid intermediates (Scheme ) 2.…”

Section: Methodsmentioning

confidence: 99%

Gold‐Catalyzed Allylation of Aryl Boronic Acids: Accessing Cross‐Coupling Reactivity with Gold

Levin

Toste

2014

Angewandte Chemie

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A sp 3 -sp 2 C-C cross-coupling reaction catalyzed by gold in the absence of a sacrificial oxidant is described. Vital to the success of this method is the implementation of a bimetallic catalyst bearing a bis(phosphino)amine ligand. A mechanistic hypothesis is presented, and observable transmetallation, C-Br oxidative addition, and C-C reductive elimination in a model gold complex are shown. We expect that this method will serve as a platform for the development of novel transformations involving redox-active gold catalysts. KeywordsGold Catalysis; C-C Coupling; Oxidative Addition; Bimetallic Catalysis; AllylationThe air-and water-stability of gold catalysts, coupled with their ability to promote complex transformations under mild conditions has attracted considerable interest from the academic community. 1 Despite the rapid pace of recent developments, the majority of gold-catalyzed processes rely on a select few reaction manifolds: (i) Lewis acid catalysis, (ii) π-activation, and (iii) the generation of carbenoid intermediates (Scheme 1A). 2 While these modes of reactivity have yielded important catalytic methodologies of broad scope and synthetic utility, 3 they are typified by catalytic cycles wherein gold maintains a +1 oxidation state, in stark contrast to the 2-electron redox cycles characteristic of late transition metal catalysis. 4 Indeed, access to Au III intermediates under catalytic conditions typically requires strong F + or I 3+ oxidants. 5,6 Despite this limitation, seminal work by Kochi and Schmidbaur has shown that Au I complexes oxidatively add alkyl halides, and are further competent to undergo C-C reductive elimination, furnishing formally cross-coupled products. 7 However, this mode of reactivity has not previously been realized in a catalytic fashion.

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“…We elected to investigate this observation. As pointed out in a recent essay,8 such unexpected experimental results have played a critical role in the advancement of organic synthesis; one ignores such “outliers” at one's own risk.…”

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confidence: 99%

Improvement in the One‐Carbon Chain Extension of Esters with Dimethylsulfoxonium Methylide

et al. 2013

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A recent report suggests that the reaction of dimethylsulfoxonium methylide with esters does not produce a chain‐extended sulfur ylide as previously reported, but rather affords the corresponding carboxylate salt. We have investigated this assertion by using a combination of ab initio molecular orbital calculations, spiking studies, and isotopic labeling. The formation of carboxylate is unambiguously demonstrated to arise through hydrolysis involving adventitious water, principally derived from moisture in commercial trimethylsulfoxonium chloride. Careful vacuum drying of this reagent diminishes the competing hydrolytic pathway resulting in higher yields for the chain‐extension reaction than previously reported.

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Black‐Swan‐Ereignisse in der organischen Synthese

Cited by 10 publications

References 160 publications

Gold‐Catalyzed Allylation of Aryl Boronic Acids: Accessing Cross‐Coupling Reactivity with Gold

Gold‐Catalyzed Allylation of Aryl Boronic Acids: Accessing Cross‐Coupling Reactivity with Gold

Gold‐Catalyzed Allylation of Aryl Boronic Acids: Accessing Cross‐Coupling Reactivity with Gold

Improvement in the One‐Carbon Chain Extension of Esters with Dimethylsulfoxonium Methylide

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Black‐Swan‐Ereignisse in der organischen Synthese

Cited by 10 publications

References 160 publications

Gold‐Catalyzed Allylation of Aryl Boronic Acids: Accessing Cross‐Coupling Reactivity with Gold

Gold‐Catalyzed Allylation of Aryl Boronic Acids: Accessing Cross‐Coupling Reactivity with Gold

Gold‐Catalyzed Allylation of Aryl Boronic Acids: Accessing Cross‐Coupling Reactivity with Gold

Improvement in the One‐Carbon Chain Extension of Esters with Dimethylsulf­oxonium Methylide

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Improvement in the One‐Carbon Chain Extension of Esters with Dimethylsulfoxonium Methylide